CN108474777A - The system and correlation method and sensor of assessment chloride concentration - Google Patents
The system and correlation method and sensor of assessment chloride concentration Download PDFInfo
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- CN108474777A CN108474777A CN201680040261.3A CN201680040261A CN108474777A CN 108474777 A CN108474777 A CN 108474777A CN 201680040261 A CN201680040261 A CN 201680040261A CN 108474777 A CN108474777 A CN 108474777A
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/38—Concrete; ceramics; glass; bricks
- G01N33/383—Concrete, cement
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N17/00—Investigating resistance of materials to the weather, to corrosion, or to light
- G01N17/02—Electrochemical measuring systems for weathering, corrosion or corrosion-protection measurement
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
- G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
- G01N27/041—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of a solid body
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
- G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
- G01N27/20—Investigating the presence of flaws
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
- G01N27/22—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating capacitance
- G01N27/24—Investigating the presence of flaws
Abstract
The present invention relates to for assessing the system in the chloride concentration of porous or composite material a presumptive area for such as reinforced concrete structure, including the sensor (1) being embedded in the presumptive area of material, it is connected to the analyzer (2) of sensor, and is connected to the processing module (4) of analyzer.Sensor (1) includes two electrodes (11) facing or coplanar, referred to as electrode, and middle layer (13) is arranged between the electrodes, the material of the presumptive area of the middle layer and structure and include calcium aluminate.Analyzer (2) is configured as applying alternating current between the electrodes and exports the impedance value or capacitance of middle layer.Processing module (4) is configured as calculating the chloride concentration assessment in the presumptive area of material by analyzer based on the impedance value exported or capacitance.
Description
Technical field
The present invention is overall about materials ' durability field, and more particularly with respect to (such as reinforcing bar in porous or composite material
Concrete, prestressed concrete or Steel-concrete Composite) cl concn assessment.The present invention exists in particular, to assessment
The sensing that the system and method and the system and method for chloride concentration in more empty or composite material presumptive areas use
Device.
Background technology
One of the main reason for Chloride Attack is armored concrete (RC) deterioration for influencing structure availability and safety.
Chlorion is the accelerating agent in rebar surface corrosion process, reduces the service life of structure.For other materials, detect that chlorion is
The indicant of seawater water proofing property or materials ' durability.
Chloride concentration of the corrosion that chloride induces on reinforcing bar reaches destruction inert protection object thin layer and (is existed by concrete
Strong basicity at the end of construction causes) threshold value when, the fender protect reinforcing bar from corrosion.After dress ornament starts, deposit
In the immature deterioration caused by various mechanism：Auxiliary area missing, steel-concrete combine missing, concrete cracking and
Layering etc..After steel corrosion starts, the physical and mechanical property of armored concrete according to the speed of environmental condition to fail.This decline
Process generates repair and the maintenance cost of bigger, is seriously affected to the performance generation of durability and life cycle.
It can be used for the risk that estimation corrosion starts in the chloride content detection of cement covering part, for optimization is tieed up
It repaiies and maintenance cost.
It is extremely complex that Chloride Attack enters the phenomenon that concrete, because it is based on multiple variables, especially concrete structure
At, its crack state and its exposure weather.
In past 30 years, the different technologies for measuring chloride are developed, and some of them are destructivenesses or invasive,
Others are non-destructive.Some of even energy original place applications.These newest technologies are to safeguard and predict armored concrete
The required technology of durability.
Most common technology is TV measuring method and voll Ha Defa (Volhard method).It is measured from the knot used
Freedom in the concrete core extracted out in structure and total chloride.However, these technologies have half destructiveness, are time-consuming and expensive mostly.
Moreover, the destructive property of these technologies leads to additional indirect cost, as traffic jam, traffic administration, road closed and
Productivity is lost, and which further increases costs.In addition, destructive property makes it impossible to measure the same position in place
, or unified samples under lab variation.
There is also non-destructive technique (Non-destructive techniques, NDT).They refer to do not change environment and
The method of the availability in the material future measured.These technologies are for example applicable in external or embedded device.By most
The usual technology of research and development is divided into following three classes：
(i) ion selective electrode (ion selective electrodes, ISE),
(ii) impedance (electrical resistivity, ER), and
(iii) fibre optical sensor (optical fiber sensor, OFS).
These three non-destructive techniques exist " Non-destructive methods for measuring chloride
ingress into concrete:Sate-5of-the-art and future challenges ", M.Torres-Luque,
E.Bastidas-Arteaga, F.Schoefs, M.Sanchez-Silva, J.F.Osma, Construction and
Building Material, Volume 68, pp 68-81 is set forth in 2014.
ISE, ER and OFS show some advantages：ISE shows good chemical stability, ER in aggressive environment
To chloride there are sensitive, OFS shows the sensibility to chloride more better than other methods.However, there are some still
The problem of not being solved.For example, in these three methods majority it is very sensitive to the condition in concrete structure (for example, temperature,
Relative humidity, pH variations), some of them need careful calibration process.
More specifically, ISE is very sensitive to the position of electrode, alkalinity and temperature.In addition, the durability of reference electrode does not have
Adapt to the validity period of concrete structure.ER is very quick to the presence, carbonization and the presence of electromagnetic field of the water content, reinforcing bar of concrete
Sense.Finally, OFS is theoretically adapted to measure low numerical value and less by such environmental effects, but optical fiber is fragile and needs volume
Outer protective case with concrete (concrete is Korrosionsmedium) to completely cut off.
Invention content
Therefore, to non-destructive and the measurement method of defect that at least partly mitigates existing NDT technologies has demand.
According to the present invention it is proposed that how empty or composite material (such as armored concrete) using a kind of being embedded into for new type
Sensor, the sensor include being adapted to collect, detect and measure the aluminic acid calcium layer from composite material free chloride ion.From
Lead to the electrical properties of this layer in gathering for above-mentioned layer by chlorion, the especially change of the impedance of layer and relative dielectric constant.
Porous or composite material the chloride concentration of sensor proximity thus can be sensor-based layer impedance and opposite be situated between
The change of electric constant and be evaluated.The layer is integrated in systems, which is set as impedance and the relative dielectric constant of measurement layer
Change, and calculate porous or composite material the chloride concentration adjacent with sensor based on these changes and assess.
More specifically, the present invention is predetermined about one for assessing porous or composite material (such as reinforced concrete structure)
The system of the chloride concentration in region, including
The sensor of embedded presumptive area,
The analyzer of the sensor is connected, and
The processing module of the analyzer is connected,
Wherein the sensor includes two electrodes facing or coplanar, referred to as electrode, is arranged among two electrodes
Middle layer, which contacts with presumptive area and includes calcium aluminate,
Wherein analyzer is set as applying alternating current between the electrodes and exports the impedance value or capacitance of middle layer, and
Wherein processing module is set as the impedance value exported based on analyzer or capacitance calculates chlorination in presumptive area
Object concentration evaluation.
In the first embodiment, electrode is the electrode faced and analyzer is set as output capacitance value.To calculate fate
Chloride concentration in domain, analytic unit are set as calculating the relative dielectric constant of the middle layer between electrode by capacitance, and
And the relative dielectric constant based on calculating calculates the chloride concentration assessment in presumptive area.
In this embodiment, the frequency of alternating current is preferably included in [100Hz, 5MHz].
In a second embodiment, analyzer be set as by apply between coplanar electrodes exchange electrical measurement coplanar electrodes it
Between impedance value, and processing module be set as the impedance value based on measurement calculate presumptive area in chloride concentration assessment.
In this embodiment, electrode is preferably coplanar electrodes.In addition, the frequency of alternating current is preferably included in
In [100Hz, 100kHz] and preferably in one of following group of frequencies：[15kHz, 37.5kHz]；[52kHz, 65kHz]；
[81kHz, 99kHz].
Present invention also contemplates that by using embedded sensor evaluation in predetermined areas is porous or composite material (such as steel
Tendon concrete structure) presumptive area in chloride concentration method, which includes two and faces or coplanar flush end
Face electrode, the middle layer being arranged between two electrodes, the material of the middle layer and the presumptive area and include aluminic acid
Calcium, this method include the following steps：
By the capacitance or impedance value that apply exchange electrical measurement middle layer between the electrodes；With
Impedance value or capacitance based on measurement calculate chloride concentration assessment in predetermined areas.
In the first embodiment, electrode be in face of electrode and measurement value be the middle layer being located between electrode electricity
Capacitance, and chloride concentration assessment is by following calculating：
The relative dielectric constant of the middle layer between electrode is calculated, and
Relative dielectric constant based on calculating calculates the chloride concentration assessment in presumptive area.
In this embodiment, the frequency of alternating current is preferably included in [100Hz, 5MHz].
In a second embodiment, the value of measurement is the impedance value of the middle layer between electrode, and chloride concentration assesses base
It is calculated in the impedance value of measurement.
In this embodiment, electrode is preferably coplanar electrodes.In addition, the frequency of alternating current is preferably included in frequency model
It encloses in [100Hz, 100kHz] and preferably in following set of frequency ranges：[16kHz, 37.5kHz]；[52kHz, 65kHz]；
[81kHz, 99kHz].
Finally, the invention further relates to the chlorine being embedded in the presumptive area of porous or composite material (such as armored concrete)
Compound sensor, including：
Shell,
At least two flat electrodes face or coplanar in shell,
Middle layer is arranged between the electrode in shell, and the middle layer is and predetermined by the hole at least one shell
The material in region and include calcium aluminate, and
Pin connector is connected to electrode via conducting wire and is arranged as connection electrode to external equipment.
In a particular embodiment, sensor includes multipair electrode, the multipair electrode along sensor axis relative to each other
Deviate and be connected to multiple pin connectors, the middle layer being arranged between the electrode of each pair of electrode and at least one arrangement
Hole in shell is open close to each pair of electrode and to middle layer.
In a particular embodiment, from following middle selection calcium aluminates：CA (=CaO.Al2O3), C3A (=3 (CaO)
.Al2O3) and C12A7(=12 (CaO) .7 (Al2O3))。
In a particular embodiment, the material of shell is glass fibre or bakelite (Bakelite) or ceramics or Teflon
(Teflon)。
Description of the drawings
It can more fully understand the present invention with reference to following description and accompanying drawings, description and accompanying drawings provide and not in an illustrative manner
It limits the scope of the invention, wherein：
- Fig. 1 is the perspective view of the embodiment of chloride sensor according to the present invention；
- Fig. 2 is the fragmentary perspective view of sensor shown in FIG. 1；
- Fig. 3 is the exploded view of sensor shown in FIG. 1；
- Fig. 4 is the vertical cross-section diagram along the IV-IV axis of Fig. 1；
- Fig. 5 is the enlarged drawing of the details A of Fig. 2；
- Fig. 6 is the schematic diagram of the system according to the present invention；
- Fig. 7 is the flow chart of the consecutive steps of first method according to the present invention；
- Fig. 8 is shown for different frequency, and CA is indicated when 0.7M NaCL solution is added CA layers at regular time
Curve of the relative dielectric constant of layer to the time；
- Fig. 9 shows curve of the relative dielectric constant to the time of CA layers of the expression of the NaCL solution for various concentration；
- Figure 10 shows the relative dielectric constant for indicating CA layers to the NaCL solution of various concentration and the song of different time
Line；
- Figure 11 shows curve of the relative dielectric constant to chloride concentration of CA layers of expression；
- Figure 12 is the flow chart of the consecutive steps of second method according to the present invention；
Figure 13 and 14, which is shown, indicates that the impedance order of magnitude and phase angle are exposed between two coplanar electrodes CA layers
The curve of the time of the whole soln of the Cl-/w of 0.50%w；
- Figure 15 and 16, which is shown, respectively indicates impedance strength | Z | and phase angle is exposed to the first of face electrode to CA layers
To electrode between 0.50%w Cl-/w whole soln time curve；
- Figure 17 and 18, which is shown, respectively indicates impedance strength | Z | and phase angle is exposed to the second of face electrode to CA layers
To electrode between 0.50%w Cl-/w whole soln time curve；
- Figure 19 shows the CA for indicating dry and is exposed between the CA of different NaCL solution, in two coplanar electrodes
Between the resistance difference Δ Z that measures to the curve of frequency；
- Figure 20 show indicate two different times t1 and t13 resistance difference Δ Z to frequency range [16kHz,
37.5kHz] in frequency curve；
- Figure 21, which is shown, indicates time average impedance discrepancy delta Z to the frequency in frequency range [16kHz, 37.5kHz]
Curve；
- Figure 22 show indicate two different times t1 and t13 resistance difference Δ Z to frequency range [52kHz,
65kHz] in frequency curve；
- Figure 23, which is shown, indicates time average impedance discrepancy delta Z to the frequency in frequency range [52kHz, 65kHz]
Curve；
- Figure 24 show indicate two different times t1 and t13 resistance difference Δ Z to frequency range [81kHz,
99kHz] in frequency curve；And
- Figure 25, which is shown, indicates time average impedance discrepancy delta Z to the frequency in frequency range [52kHz, 65kHz]
Curve.
Specific implementation mode
Such as subsequent descriptions, the present invention is used for concrete structure, such as armored concrete, prestressed concrete or steel-mix
Solidifying soil mixed structure.Certainly, present invention can apply to other porous or composite materials.
Although illustrative embodiments can have various modifications and substitute mode, embodiment is thus in the accompanying drawings to show
The mode of example shows and will be described in detail herein, it being understood, however, that there is no limited with disclosed particular form
The intention of illustrative embodiments processed, on the contrary, illustrative embodiments cover all variations within the scope of the claims, etc.
Same and replacement.Same numbers in all description of the drawings refer to similar elements.
Before discussing illustrative embodiments in more detail, it should be noted that some illustrative embodiments are described as process
Or the method described with flow chart.Although flow chart describes to operate with sequential process, many operations can concomitantly or together
When parallel execute.In addition, the sequence of operation can rearrange.Process can be terminated when its operation is completed, but equally may be used
It is not included in step in attached drawing to have.Process can be with corresponding method, function, process, subprocess, auxiliary program etc..
Method discussed below, some of them illustrate that this method can pass through hardware, software, firmware, centre with flow chart
Equipment, microcoding hardware description language or any its composition are realized.When in software, firmware, middleware or microcoding
When realization, executing the program code of necessary task, either code segment can be stored in machine or computer-readable medium, such as
In storage medium.Processor can execute necessary task.Specific structure disclosed herein and function details is only to represent
Property, for the purpose of describing exemplary embodiments of the present invention.However, the present invention can be implemented in the form of multiple replacements
And it is not necessarily to be construed as being limited only to embodiment described herein.
Specialized vocabulary used herein is only for the purpose of describing specific implementation mode and not limit exemplary implementation
Mode.Singulative " one " used herein, "one", " and ", "the", be intended to include same plural form, unless on
Hereafter clearly illustrate other meanings.It will be further understood that the term "comprising", " including ", " comprising ", and/or " packet
Include ", as used herein, refer to feature, integer, step, operation, element and/or the element in the presence of statement, but be not excluded for
In the presence of or additional one or more of the other feature, integer, step, operation, element, component and/or a combination thereof.Similarly, it answers
Notice that term " coupling " should not be construed as limiting to only to be directly connected to.Therefore, the range of phrase " the equipment B for being coupled to device A "
It should not be limited to equipment or system that wherein output equipment A is directly connected to input equipment B.Its indicate there are output equipment A with
Path between input equipment B can be the path for including other equipment or method.Unless otherwise defined, make herein
Whole terms (including technical and scientific term) meaning having the same, such as the technology of illustrative embodiments fields
The common understanding of personnel.It will be further understood that the term for example limited jointly with dictionary, should be interpreted that with meeting its related skill
Meaning under art background and not with the meaning interpretation of idealization or over formalization, unless specific so limit herein
It is fixed.
According to the present invention it is proposed that new embedded type sensor, includes being reacted with the free chloride ion from concrete structure
Certain layer, which causes the change of the electrical properties (impedance, electric conductivity and relative dielectric constant) of layer.Into sensor
Therefore the amount of chloride can be estimated by electrical property change.According to the present invention, certain layer includes calcium aluminate.
Fig. 1 to 5 shows the embodiment of sensor according to the present invention.
Chloride sensor 1 includes shell 10, is made of three parts 10a, 10b and 10c.Because sensor is to be considered as
Insertion in concrete, should be able to be towards the environment (temperature of concrete, humidity, residual mechanical stress) in concrete.Shell needs
Want can to bear the high-strength material of the environmental condition.In a preferred embodiment, shell 10, which has, usually shows good object
The fibrous glass matrix with chemical characteristic of reason.Other materials can be used, such as bakelite or Teflon.
More specifically, shell 10 includes lower part 10a, middle part 10b and top 10c.Lower part 10a and top 10c is printing
Circuit board.The conductive electrode 11 of copper or golden material, is printed on the lower surface of top 10c and the upper surface of lower part 10a.Hole
12, by calcium aluminate powder is made and be full of in middle part 10b, form aluminic acid calcium layer 13.In this embodiment, electrode 11
Shape with hole 12 is rectangle.
Electrode 11 and hole 12 are relatively positioned, and are made when three parts are assembled together, each electricity of top 10c
Pole 11 faces toward the electrode 11 of 10b, and the hole 12 of aluminic acid calcium layer is located between two electrodes.
In the embodiment shown in Fig. 1 to 5, sensor includes eight pairs of electrodes faced 11 and four filling aluminic acid calcium layer
Hole.The electrode that four couple of electrode and two row that two couple that eight pairs of electrodes faced are divided into four rows faces faces, fills calcium aluminate
The hole 12 (forming chamber) of layer is with the electrode of often row faced to being associated with.
In the drawings, two pairs of electrodes 11 faced are associated with the same hole 12 (or room) so that same calcium aluminate
13 (so-called middle layer) of layer are present between the electrode of the two electrodes pair.
Top 10c and/or and/or lower part 10a in hole 14 is made so that when sensor be embedded in concrete structure in when,
Middle layer 13 is contacted with concrete via hole 14.In the illustrated embodiment, in the hole 14 and lower part 10a in the 10c of top
A hole 14 electrode that every row is faced be made and lead to a hole 12 of middle part.In each part 10a or 10c,
Hole 14 is offset horizontally from relative to each other to contact the interlaced area of concrete.Each hole 14 is centered in coplanar electrodes 11
Between.
In addition, each electrode 11 of upper and lower part is connected to the pin connector 15 pin connector quilt via conducting wire 16
It is considered as connection electrode 11 to external device (ED).
As described above, each filling of hole 12 includes the powder of calcium aluminate.The powder be for example including a calcium aluminate CA (=
CaO.Al2O3) or three calcium aluminate C3A (=3 (CaO) .Al2O3) or C12A7Or powder or mixing including the calcium aluminate powder
End.
Fig. 5 is the diagram of the size of the different elements for the sensor for showing then to illustrate herein.In middle part
The size of rectangular opening 12 is that the size of c*d and rectangular electrode is a*b.Only a part of a'*b of electrode 11a, which is exposed to, is present in
Middle layer in hole 12.Hole 14 is that round and its diameter is 6 Ethylmercurichlorendimides (10-10m).The diameter is more than (several angstroms of hydrone diameter
Rice), the pore diameter (about 1000 Ethylmercurichlorendimide) of chlorion diameter (a few Ethylmercurichlorendimides) and concrete.Therefore hydrone and chlorion can be into
Enter sensor or reaches middle layer via hole 14.
As shown in fig. 6, the insertion of sensor 1 includes the reinforced concrete structure RC of reinforcing bar SB.Sensor 1 is vertically embedded in
In reinforced concrete structure, perpendicular to the outer wall of reinforced concrete structure, to measure the different depth in reinforced concrete structure
Chloride concentration.These measurements changed at one are executed by connecting sensor 1 to analyzer 2 via connecting line 3.Becoming
Change in example, can be horizontally set to measure the chloride content in certain depth.
These are measured is executed by connecting sensor 1 to analyzer 2 via connecting line 3.Analyzer 2 is connected to processing module
4。
In the first embodiment of the present invention, the capacitance of the middle layer between the electrode faced based on two calculates chlorination
Object concentration evaluation.In the present embodiment, analyzer 2 is capacitance analysis device.
In second embodiment of the present invention, the resistance of the middle layer between electrode faced based on two or coplanar
Anti- value calculates chloride concentration assessment.In this second embodiment, analyzer 2 is impedance analyzer.
The two embodiments will be described in more detail below.
First embodiment
In this embodiment, using the method for assessing chloride concentration of sensors described above in Fig. 7
Flow chart in be described in detail.
In first step S1, sensor 1 measures the capacitance C between each pair of electrode 11 faced.Capacitance by
Apply exchange electrical measurement between electrode.The capacitance is measured by analyzer 2.
In second step S2, relative permittivity value ε is calculated from capacitance C following equationr：
Wherein：
-ε0It is permittivity of vacuum (ε0=8.85 × 10-12F/m)；
- d is two interelectrode distances, and
- S is the area (S=a'*b) that electrode is exposed to aluminic acid calcium layer.
Relative dielectric constant ε is calculated by analyzer 2 and/or processing module 4r。
In third step S3, relative permittivity value ε is based on by processing module 4rCalculate chloride concentration assessment.
In this embodiment, analyzer 2 is for example to be coupled to dielectric test fixture (Dielectric test
Fixture) Agilent (Agilent) 4294A analyzers of 16451B.To the particular device, frequency range can be applied to
The alternating current of 100Hz-5MHz, ceiling voltage 0.5V directly measure capacitance.
This method is tested by using the sensor as shown in Fig. 1 to 5.It is exposed to the area of the electrode of middle layer 13
S is 1.13x 10-3m2.Experiment is realized at a temperature of 19 DEG C ± 1 DEG C.Middle layer 13 passes through following completions：In each hole (room) 12
Mono- calcium aluminate powders (CA) of middle addition 6.6g are simultaneously tamped with mallet is smash during 120 seconds, until it reaches 1.84x 10-3M and 2.27x
10-3Thickness between m.
Deionized water (0M) and tool there are three types of different NaCl concentrations three kinds of NaCl solutions for test 0.5M, 0.7M and
The dielectric behavior of mono- aluminic acid calcium layer of 1.0M (CA layers).
Table 1 lists the title and feature of each test.
Table 1
In addition, after 1ml (milliliter) NaCl solution is added to CA 1 minute and execute within every 10 minutes in 1 hour measure with
Determine time dependence.Each experiment executes three times.NaCl solution introduces sensor by hole 14.
Fig. 8 displays indicate, when the NaCl solution of every ten minutes addition 1ml 0.7M, to calculate different ac frequencies
CA layers relative dielectric constant to the figure of time.Initially, CA layers are dry.
All these figures show identical trend.In initial 10 minutes of each experiment, relative dielectric constant arrives
The value is kept up to stationary value and approximatively until measurement period terminates.When these illustrate relative dielectric constant and are both not dependent on
Between be also not dependent on frequency in the frequency range.
Fig. 9 shows relative dielectric constant with the increased variation of chloride solution concentration.The effect of chloride solution is to improve
The relative dielectric constant measured.Its indicate, the entrance of the Cl and Na ions due to causing ionic polarization in material, electrode it
Between capacitance increase.
Figure 10 and Figure 11 shows CA layers of relative dielectric constant εrIt is proportional according to following relationships to its chlorine ion concentration：
εr=2.438+1.391X (1)
Wherein:εrRelative dielectric constant and X be chloride molar concentration.
More specifically, Figure 10 shows chloride to the CA of the drying of measurement and is exposed to 0M, 0.5M, 0.7M and 1M NaCl
The effect of the relative dielectric constant of the CA of solution, and Figure 11 shows correlation between chloride concentration and relative dielectric constant.
It indicates that the ionic polarization of NaCl and the molecular polarization of water lead to higher dielectric constant values, allows to increase in CA
Storage charge.In addition, ion penetration leads to the reduction of resistivity into material, and of course, the increase of electric conductivity.
Second embodiment
In this embodiment, using the method for assessing chloride concentration of sensors described above in Figure 12
Flow chart in elaborate.
In first step S'1, sensor 1 measures the impedance value between electrode 11 each pair of facing or coplanar.
By applying exchange electrical measurement impedance value between two electrodes.The impedance value is measured by analyzer 2.
In second step S'2, chloride concentration assessment is calculated by impedance value of the processing module 4 based on measurement.
In this embodiment, analyzer 2 is the Agilent 4294A for being for example coupled to Kelvin clip 16089A
Analyzer.The instrument is in the frequency range of 100Hz-100kHz, with 0.5V voltage power supplies.Due to CA show in fig. 8 it is steady
Determine state, the reduction in the frequency is possible.
This method is by by using sensor experiment same as the first embodiment.
During the experiment, the face electrode 11 adjacent with CA layers of two couple contacted measured in the same hole 12 faces electricity
Impedance value between pole and coplanar electrodes, i.e., 4 measurements：
1 measurement between the electrode of first pair of electrode faced 11；
1 measurement between the electrode of second pair of electrode faced 11；
1 measurement between the electrode of first pair of coplanar electrode 11；
1 measurement between the electrode of second pair of coplanar electrode 11.
Two pairs are measured, opposite behavior of the impedance display to chloride concentration, that is, impedance value is with chloride concentration
Increase and reduces.
Table 2 lists the experiment for calibration process, and table 3 shows the randomization of these experiments.Solution concentration exists
Change between the 0% and 6%w of the Cl-/w of whole soln, and for Demonstrate Design applicability, a sensor is empty
(NCA).Solution is directly added to hole 14 with rubber tube and syringe, and due to time of measuring (substantially 20 seconds), (is filled in each room
Fill out CA layers of hole 12) measure two side by side capacitor (in face of electrode between) and only one coplanar capacitor (in coplanar electricity
Between pole).The main purpose of the design is to determine linear, time response and sensitivity.Each solution quilt shown in table 3
It makes 4 times.It amounts to, we used 22 equipment, are repeated 4 times, and measure 13 times at any time.In addition, when testing beginning
We measure the impedance of dry CA.
Design of the table 2. for the experiment of calibration
The randomization that table 3. is tested
Figure 13 shows impedance and the phase angle of the sensor of the CA layers of the whole soln with the Cl-/w for being exposed to 0.50%w
Behavior, these measured values are derived between coplanar electrodes.At 0 minute, CA was dry, and its phase angle shows its capacitance
Property (≈ -90 °).However, when solution is reacted with CA, angular phasing changes until reaching -5 °.This indicates that CA is no longer pure electricity
Hold, and also becomes resistance.
On the other hand, when the amplitude of impedance is shown in chloride solution and aluminic acid reactant salt its impedance on the order of magnitude from 10
These results meet " Study of the dielectric properties in the NaNbO3-KNbO3-
In2O3system using AC impedance spectroscopy ", E.Atamanik and V.Thangadurai, 2009,
Materials Research Bulletin 44(4):Result of study disclosed in 931-936.In this study, difference is analyzed
The capacitance of ceramic material and the behavior of impedance.It is decreased to 103 Ω.Last dielectric constant is limited by following equation：
ε=ε '+j ε " (2)
Wherein
- ε ' and ε " is the real and imaginary parts of dielectric constant；
- Z, Z ' and Z " are the amount of impedance, real and imaginary parts；
- S is the area that electrode is exposed to CA,
- d is interelectrode distance,
- f is frequency, and
- ε 0 is permittivity of vacuum (8,8542x 10-12C2/Nm2)。
As equation (3) and (4) illustrate, for dielectric constant to impedance inversely related, this is consistent with previous result.
In contrast, same room (hole 12 of same filling CA floor) plane-parallel capacitor (in face of electrode between) show
Show different as a result, being shown by Figure 15 to 18.
Figure 15 and Figure 16 expressions are faced by being exposed to separated the first couple of the CA layers of the Cl-/w whole solns of 0.50%w
Electrode (first side by side capacitor) impedance value | Z | and the Bode diagram at phase angle.Figure 17 and Figure 18 is indicated similarly by being exposed to
The figure of electrode that same CA layers of separated the second couple of the Cl-/w whole solns of 0.50%w face (second side by side capacitor).
Even if when two side by side capacitor have and (the resistance sexual behaviour to coplanar capacitor and pair simultaneously of coplanar capacitor
Arrange the capacitance sexual behaviour of capacitor) identical variation when, end up in experiment, capacitor is not up to similar complete electricity side by side
Resistive behavior, (referring to Figure 16 and Figure 18) as aluminate has in coplanar plane-parallel capacitor.In addition, testing
Period, the impedance magnitude in a capacitor reach stable state with the change of time in another capacitor middle impedance
(Figure 15 and Figure 17).The difference can pass through the additional symbols of diffusion process.
This be in this impedance measurement embodiment, preferably measure coplanar electrodes between impedance the reasons why.
Baseline results are shown, to coplanar electrodes, in initial dry CA (Z0) and are exposed to solution (0.5,1.5 and 6.0%w
Cl-/w whole soln) CA between resistance difference Δ Z reach stable state after 15kHz, as shown in figure 19.Δ Z passes through
Following calculating：
Δ Z=Z-Z0 (4)
Additionally, there are the ranges that some response signals show a large amount of noise：37.6-52kHz and 65.1-80.9kHz.It must
It must avoid measuring impedance with these ranges.Therefore, it measures and is advantageously carried out in following ranges：
16kHz<f<37.5kHz
52kHz<f<65kHz
81kHz<f<99kHz
In addition, about time response, one should note that, in the final resistance difference of 90 minutes (t13) and at 2 minutes
(t1) significant difference is not present between the first resistance difference, as shown in Figure 20 to 25.Figure 20 indicate for C15t1, C15t13,
The resistance difference Δ Z of C17t1, C17t13, C21t1, C21t13 are in frequency range [16kHz；37.5kHz] in frequency, and
And Figure 21 indicates the time average impedance difference of t1 to t3 (to C15, C17 and C21) at any time.Figure 22-23 and Figure 24-25 is indicated
Similarly respectively for frequency range [52kHz；65kHz] and [81kHz；99kHz] figure.
These curve graph (Figure 20 to 25) display frequency ranges [16kHz；37.5kHz]、[52kHz；65kHz] and
[81kHz；99kHz] when measuring impedance between coplanar electrodes it is best suited for alternating current.In these frequency ranges
Alternating current, chloride concentration can be assessed by the impedance between coplanar electrodes measured.
The major advantage of the above method and system is：
Sensor is chemically stable (to the alkalinity in concrete),
Sensor can with bearing temperature and mechanical stress,
Sensor does not need Additional Protection, because shell can detach internal material from corrosive environment,
Anywhere sensor can be placed, close corner,
Measurement is not influenced by existing for electric field,
Its structure is cheap.
Certainly, chloride sensor 1 is not necessarily to include simultaneously the electrode faced and coplanar electricity to the room of same filling calcium aluminate
Pole.Such as with the method based on capacitance measurement, it is enough that sensor only has the electrode faced on room both sides.If using base
In the method for impedance measurement, sensor is only with coplanar electrodes in the side of room with the electrode faced or only on the both sides of room
Enough.
Although some embodiments of the present invention have been shown in the accompanying drawings and have described in previous embodiment, answer
When understand the present invention is not limited to disclosed embodiments, and can have it is multiple without departing from such as aforementioned present invention with have the right to want
Ask variation, change and the replacement for limiting range.
Claims (16)
1. the system of the chloride concentration for assessing porous or composite material a presumptive area, including
Sensor (1), is embedded in the presumptive area,
Analyzer (2) is connected to the sensor, and
Processing module (4), is connected to the analyzer,
Wherein, the sensor (1) includes two flat electrodes (11) facing or coplanar, referred to as electrode, middle layer
(13) arrangement between said electrodes, the material of the middle layer and the presumptive area and include calcium aluminate,
Wherein, the analyzer (2) is configured as the resistance for applying alternating current between said electrodes and exporting the middle layer
Anti- value or capacitance, and
Wherein, the processing module (4) is configured as calculating based on the impedance value exported by the analyzer or capacitance
Chloride concentration assessment in the presumptive area.
2. system according to claim 1, wherein the electrode (11) is the electrode faced, and wherein, the analysis
Instrument is configured as output capacitance value, and wherein, in order to calculate the assessment of the chloride concentration in the presumptive area, institute
Processing module (4) is stated to be configured as from the capacitance that is exported by the analyzer calculates between said electrodes described
The relative permittivity value of interbed, and the relative permittivity value based on calculating calculates the chlorine in the presumptive area
Compound concentration evaluation.
3. system according to claim 2, wherein the frequency of the alternating current is included in [100Hz, 5MHz].
4. system according to claim 1, wherein the analyzer (2) is configured as by applying between said electrodes
Add the impedance value of exchange electrical measurement between said electrodes, and the processing module (4) is configured as the impedance based on measurement
Value calculates the chloride concentration assessment in the presumptive area.
5. system according to claim 4, wherein the electrode is coplanar electrodes.
6. system according to claim 4 or 5, wherein the frequency of the alternating current is included in the group of following frequency ranges
In：
[100Hz, 100kHz]；
[16kHz, 37.5kHz]；
[52kHz, 65kHz]；
[81kHz, 99kHz].
7. the method for assessing the chloride concentration in porous or composite material presumptive area, by using being embedded in
The sensor in presumptive area is stated, the sensor includes the electrode of two planar end surfaces facing or coplanar, is arranged in two
Middle layer between a electrode, the material of the middle layer and the presumptive area and include calcium aluminate,
The method includes following step：
By applying exchange electrical measurement (S1 between said electrodes；S'1) the capacitance or impedance value of the middle layer；And
And
Impedance value or capacitance based on measurement calculate (S2, S3；S'2) the chloride concentration assessment in the presumptive area.
8. according to the method described in claim 7, wherein, the electrode is the electrode faced and measured value is described
The capacitance of the middle layer between electrode, and wherein, the chloride concentration assessment is by following calculating：
The relative permittivity value of the middle layer of (S2) between said electrodes is calculated, and
Relative permittivity value based on calculating calculates the chloride concentration assessment in (S3) described presumptive area.
9. according to the method described in claim 8, wherein, the frequency of the alternating current is included in [100Hz, 5MHz].
10. according to the method described in claim 7, wherein, measured value is the middle layer between said electrodes
Impedance value, and wherein, the chloride concentration assessment is calculated based on measured impedance value.
11. according to the method described in claim 10, wherein, the electrode is coplanar electrodes.
12. according to the method for claim 11, wherein the frequency of the alternating current is included in the group of following frequency ranges
In：
[100Hz, 100kHz]；
[16kHz, 37.5kHz]；
[52kHz, 65kHz]；
[81kHz, 99kHz].
13. the chloride sensor of porous or composite construction the presumptive area of insertion, including：
Shell (10),
- at least two flat electrodes face or coplanar, referred to as electrode (11), in the shell,
Middle layer (13) is arranged between the electrode in the shell, and the middle layer is via at least one shell
In hole and the presumptive area material, and include calcium aluminate, and
Pin connector (15) is connected to the electrode via conducting wire and arranges that (16) are to connect the electrode to outside to fill
It sets.
14. chloride sensor according to claim 13, wherein the chloride sensor includes multipair along described
Electrode (11) that is that the axis of sensor deviates relative to each other and being connected to multiple pin connectors, is arranged in the institute of each pair of electrode
The middle layer (13) between electrode is stated, and close to each pair of electrode arrangement and is open to the centre in the shell (10)
At least one hole (14) of layer.
15. the chloride sensor according to any one of claim 13 to 14, wherein the calcium aluminate is selected from following
Group：
- CA,
-C3A,
-C12A7。
16. the chloride sensor according to any one of claim 13 to 15, wherein the material of the shell (10) is
Glass fibre or bakelite or ceramics or Teflon.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP15306128.8A EP3115781B1 (en) | 2015-07-09 | 2015-07-09 | System for assessing chloride concentration and corresponding method and sensor |
| EP15306128.8 | 2015-07-09 | ||
| PCT/EP2016/066212 WO2017005885A1 (en) | 2015-07-09 | 2016-07-07 | System for assessing chloride concentration and corresponding method and sensor |
Publications (2)
| Publication Number | Publication Date |
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| CN108474777A true CN108474777A (en) | 2018-08-31 |
| CN108474777B CN108474777B (en) | 2021-04-30 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201680040261.3A Active CN108474777B (en) | 2015-07-09 | 2016-07-07 | System for evaluating chloride concentration and corresponding method and sensor |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US10488389B2 (en) |
| EP (2) | EP3115781B1 (en) |
| CN (1) | CN108474777B (en) |
| CA (1) | CA2990750C (en) |
| DK (1) | DK3115781T3 (en) |
| ES (1) | ES2683618T3 (en) |
| PT (1) | PT3115781T (en) |
| WO (1) | WO2017005885A1 (en) |
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| CN109358098A (en) * | 2018-12-25 | 2019-02-19 | 厦门市建筑科学研究院集团股份有限公司 | A method of test cement-based material surface chlorine ion concentration |
| CN110836631A (en) * | 2019-11-22 | 2020-02-25 | 青岛理工大学 | Device and method for detecting steel bars in concrete |
| CN113092743A (en) * | 2021-04-02 | 2021-07-09 | 中国建材检验认证集团北京天誉有限公司 | Cement product whiskering test equipment and whiskering degree detection method |
| WO2022199224A1 (en) * | 2021-03-22 | 2022-09-29 | 青岛理工大学 | Sensing apparatus for synchronous transport of moisture and chloride ions inside concrete |
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| US11815504B2 (en) * | 2016-07-11 | 2023-11-14 | Quipip, Llc | Sensor device, and systems and methods for obtaining measurements of selected characteristics of a concrete mixture |
| US10449721B2 (en) | 2017-10-11 | 2019-10-22 | Deborah D. L. Chung | Systems and method for monitoring three-dimensional printing |
| CN107807148A (en) * | 2017-10-23 | 2018-03-16 | 河海大学 | Outsourcing AEM build-in type concrete chloride ion sensor and preparation and method of testing |
| US10620062B2 (en) | 2017-10-23 | 2020-04-14 | Deborah D. L. Chung | Cement-based material systems and method for self-sensing and weighing |
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Also Published As
| Publication number | Publication date |
|---|---|
| ES2683618T3 (en) | 2018-09-27 |
| CN108474777B (en) | 2021-04-30 |
| US10488389B2 (en) | 2019-11-26 |
| DK3115781T3 (en) | 2018-08-13 |
| WO2017005885A1 (en) | 2017-01-12 |
| EP3115781B1 (en) | 2018-06-27 |
| US20190107525A1 (en) | 2019-04-11 |
| PT3115781T (en) | 2018-10-26 |
| EP3320337A1 (en) | 2018-05-16 |
| EP3115781A1 (en) | 2017-01-11 |
| CA2990750C (en) | 2023-04-04 |
| CA2990750A1 (en) | 2017-01-12 |
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